EP1689735B1 - Method for producing glycerol carbonate methacrylate - Google Patents
Method for producing glycerol carbonate methacrylate Download PDFInfo
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- EP1689735B1 EP1689735B1 EP04764403A EP04764403A EP1689735B1 EP 1689735 B1 EP1689735 B1 EP 1689735B1 EP 04764403 A EP04764403 A EP 04764403A EP 04764403 A EP04764403 A EP 04764403A EP 1689735 B1 EP1689735 B1 EP 1689735B1
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- Prior art keywords
- methyl methacrylate
- butyl
- dioxolan
- oxo
- preparing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the invention relates to a process for the preparation of glycerol carbonate methacrylate in the presence of metal-chelate catalysts of the metal-1,3-diketonate type, in particular zirconium acetylacetonate.
- glycerol carbonate methacrylate (2-oxo-1,3-dioxolan-4-yl) methyl methacrylate (glycerol carbonate methacrylate) is a widely used crosslinker.
- Various production methods for glycerol carbonate methacrylate are known.
- JP 2001018729 Glycerine carbonate is reacted with acrylic acid chloride.
- the accumulating chloride waste represents a major environmental impact WO 2000031195 glycidyl methacrylate is reacted with CO 2 .
- This process is carried out under high pressure. The necessary process equipment is complicated and expensive.
- DE 3937116 For example, a cyclocarbonate-containing alcohol is reacted with a carboxylic acid at elevated temperature and in the presence of an acidic catalyst.
- the desired product is obtained after distillation in a purity of 75.5%.
- the yield varies between 25.5 and 83%, depending on the acid used. With the purity of only 75.5% achieved here, the product can not be used in many applications.
- the object of the invention was to produce glycerol carbonate methacrylate in high purity and with high yields.
- the object was achieved by a process for the preparation of (2-oxo-1,3-dioxolan-4-yl) methyl methacrylate, in which methyl methacrylate in the presence of stabilizers and a metal ion-1,3-diketonate metal chelate catalyst , in particular zirconium acetylacetonate is transesterified with glycerol carbonate.
- zirconium acetylacetonate as catalyst allows very mild conditions to be used.
- the transesterification in the presence of Zirkonacetylacetonat takes place at 50-80 ° C, preferably at 70 ° C.
- Zirconium acetylacetonate is preferably used in amounts of 0.1-5.0 wt .-%, particularly preferably of 1.0-3.0 wt .-%, based on the total weight of the mixture.
- metal 1,3-diketonates e.g. Lithium or zinc 1,3-diketonates or 1,3-diphenylpropane-1,3-dione.
- a low crosslinker content is achieved by the reaction procedure according to the invention.
- a low crosslinker content has an effect in applications in that improved mechanical properties are achieved in the copolymerization with other monofunctional monomers.
- the material is less brittle.
- crosslinkers glycerol dimethacrylate and glycerol trimethacrylate are observed.
- a content of less than 5% by weight, more preferably less than 3% by weight, of crosslinking agent is observed in the product.
- the product can be produced in high yields and in high purity. It yields over 80% are achieved, with purities of the product of about 90%. Due to the purities achieved can be dispensed with a costly distillative cleaning.
- the monomer has a high boiling point and can therefore only be separated in a high vacuum. It eliminates a complicated distillation apparatus and the risk of polymerization due to the high thermal load, which is often observed in this monomer.
- a tocopherol compound is used for the stabilization of ethylenically unsaturated monomers.
- tocopherol is in 2-position by a 4,8,12-trimethyltridecyl radical substituted chroman-6-ols (3,4-dihydro-2 H- 1-benzopyran-6-ols ).
- the tocopherols which can preferably be used according to the invention include alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol, zeta2-tocopherol and eta-tocopherol, all of the abovementioned compounds in each case in the (2R, 4'R, 8'R) - Form, as well as alpha-tocopherol in the (all-rac) form.
- alpha-tocopherol in the (2R, 4'R, 8'R) form (common name: RRR-alpha-tocopherol) and also the synthetic racemic alpha-tocopherol (all-rac-alpha-tocopherol).
- RRR-alpha-tocopherol common name: RRR-alpha-tocopherol
- all-rac-alpha-tocopherol all-rac-alpha-tocopherol
- the proportion of stabilizers individually or as a mixture is generally 0.01-0.50 wt .-%, wherein the concentration of the stabilizers is preferably selected so that the color number is not impaired according to DIN 55945. Many of these stabilizers are commercially available.
- Glycerol carbonate methacrylate can be used as a functional monomer in copolymers of paints and adhesives, with which a subsequent, polymer-analogous reaction, inter alia, the crosslinking with difunctional amines in a paint formulation, is possible. In addition, can it can be used in battery electrolytes, extrusion resins and for metal extraction.
- 118 g (1.0 mol) of glycerol carbonate are heated with 600 g (6.0 mol) of methyl methacrylate and 0.14 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl (Tempol) in a round bottom flask with distillation apparatus. Any existing water is distilled off azeotropically with methyl methacrylate. The mixture is then cooled slightly. 18.0 g of zirconium acetylacetonate and the amount of methyl methacrylate equivalent to the azeotrope distillate are added to the mixture. The mixture is heated to boiling. The alcoholysis is started at 70 ° C head temperature. Towards the end of the reaction it increases to 100 ° C.
- the mixture is cooled and the catalyst zirconium acetylacetonate precipitated with dilute phosphoric acid. Subsequently, the suspension is passed through a pressure filter and the filtrate is separated.
- the filtrate is shaken out in a separating funnel with a dilute NaCl solution.
- the filtrate is degassed on a rotary evaporator at 70 ° C and 200-10 mbar.
- the mixture is cooled and the catalyst zirconium acetylacetonate precipitated with dilute phosphoric acid. Subsequently, the suspension is passed through a pressure filter and the filtrate is separated.
- the filtrate is shaken out in a separating funnel with dilute NaCl solution.
- the filtrate is degassed on a rotary evaporator at 70 ° C and 200-10 mbar.
- the mixture is then cooled, passed through a pressure filter and the filtrate is separated.
- the filtrate is shaken out in a separating funnel with dilute NaCl solution.
- the filtrate is degassed on a rotary evaporator at 70 ° C and 200-10 mbar.
- test results are summarized in the following table: attempt catalyst Rohester Monomer pure (MMA containing) GC: * Quantity on% approach alcohol product HS1 HS2 Polytest in MeOH yield alcohol product HS1 HS2 FI% FI% FI% FI% % d. Th.
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Glycerincarbonatmethacrylat in Gegenwart von Metall-Chelat-Katalysatoren vom Typ Metallion-1,3-Diketonat, insbesondere Zirkonacetylacetonat.The invention relates to a process for the preparation of glycerol carbonate methacrylate in the presence of metal-chelate catalysts of the metal-1,3-diketonate type, in particular zirconium acetylacetonate.
In der Lackindustrie ist (2-Oxo-1,3-dioxolan-4-yl)methylmethacrylat (Glycerincarbonatmethacrylat) ein viel verwendeter Vernetzer. Es sind verschiedene Herstellverfahren für Glycerincarbonatmethacrylat bekannt.In the paint industry, (2-oxo-1,3-dioxolan-4-yl) methyl methacrylate (glycerol carbonate methacrylate) is a widely used crosslinker. Various production methods for glycerol carbonate methacrylate are known.
In
Aufgabe der Erfindung war es Glycerincarbonatmethacrylat in hoher Reinheit und mit hohen Ausbeuten herzustellen.The object of the invention was to produce glycerol carbonate methacrylate in high purity and with high yields.
Die Aufgabe wurde gelöst durch ein Verfahren zur Herstellung von (2-Oxo-1,3-dioxolan-4-yl)methylmethacrylat, bei dem Methylmethacrylat in Gegenwart von Stabilisatoren und eines Metall-Chelat-Katalysators vom Typ Metallion-1,3-Diketonat, insbesondere Zirkonacetylacetonat mit Glycerincarbonat umgeestert wird.The object was achieved by a process for the preparation of (2-oxo-1,3-dioxolan-4-yl) methyl methacrylate, in which methyl methacrylate in the presence of stabilizers and a metal ion-1,3-diketonate metal chelate catalyst , in particular zirconium acetylacetonate is transesterified with glycerol carbonate.
Überraschend wurde gefunden, dass durch den Einsatz von Zirkonacetylacetonat als Katalysator unter sehr milden Bedingungen gearbeitet werden kann. Die Umesterung in Gegenwart von Zirkonacetylacetonat erfolgt bei 50-80°C, bevorzugt bei 70°C.Surprisingly, it has been found that the use of zirconium acetylacetonate as catalyst allows very mild conditions to be used. The transesterification in the presence of Zirkonacetylacetonat takes place at 50-80 ° C, preferably at 70 ° C.
Zirkonacetylacetonat wird bevorzugt in Mengen von 0,1-5,0 Gew.-%, besonders bevorzugt von von 1,0-3,0 Gew.-%, bezogen auf das Gesamtgewicht des Ansatzes, eingesetzt.Zirconium acetylacetonate is preferably used in amounts of 0.1-5.0 wt .-%, particularly preferably of 1.0-3.0 wt .-%, based on the total weight of the mixture.
Als Katalysator können neben Zirkonacetylacetonat auch andere Metall-1,3-Diketonate, wie z.B. Lithium- oder Zink-1,3-Diketonate oder 1,3-Diphenylpropan-1,3-dion verwendet werden.In addition to zirconium acetylacetonate, other metal 1,3-diketonates, e.g. Lithium or zinc 1,3-diketonates or 1,3-diphenylpropane-1,3-dione.
Es wurde gefunden, dass durch die erfindungsgemäße Reaktionsführung ein niedriger Vernetzergehalt erzielt wird. Ein niedriger Vernetzergehalt wirkt sich in Anwendungen dadurch aus, dass verbesserte mechanische Eigenschaften bei der Copolymerisation mit anderen monofunktionellen Monomeren erzielt werden. Das Material ist weniger spröde. Als Vernetzer werden Glycerindimethacrylat und Glycerintrimethacrylat beobachtet. Vorzugsweise wird im Produkt ein Gehalt von weniger als 5-Gew.-%, besonders bevorzugt von weniger als 3 Gew.-%, Vernetzer beobachtet.It has been found that a low crosslinker content is achieved by the reaction procedure according to the invention. A low crosslinker content has an effect in applications in that improved mechanical properties are achieved in the copolymerization with other monofunctional monomers. The material is less brittle. As crosslinkers, glycerol dimethacrylate and glycerol trimethacrylate are observed. Preferably, a content of less than 5% by weight, more preferably less than 3% by weight, of crosslinking agent is observed in the product.
Außerdem wurde gefunden, dass das Produkt mit hohen Ausbeuten und in hoher Reinheit hergestellt werden kann. Es werden Ausbeuten über 80% erzielt, mit Reinheiten des Produktes von ca. 90%. Durch die erzielten Reinheiten kann auf eine aufwendige destillative Reinigung verzichtet werden. Das Monomer besitzt einen hohen Siedepunkt und ist daher nur im Hochvakuum abtrennbar. Es entfällt eine aufwendige Destillationsapparatur und die Gefahr der Polymerisation durch die hohe thermische Belastung, was bei diesem Monomer häufig beobachtet wird.In addition, it has been found that the product can be produced in high yields and in high purity. It yields over 80% are achieved, with purities of the product of about 90%. Due to the purities achieved can be dispensed with a costly distillative cleaning. The monomer has a high boiling point and can therefore only be separated in a high vacuum. It eliminates a complicated distillation apparatus and the risk of polymerization due to the high thermal load, which is often observed in this monomer.
Bei der Herstellung von (2-Oxo-1,3-dioxolan-4-yl)methylmethacrylat werden Stabilisatoren zugefügt, die eine radikalische Polymerisation der (Meth)acrylgruppen während der Reaktion verhindern. Diese Stabilisatoren sind in der Fachwelt weithin bekannt.In the preparation of (2-oxo-1,3-dioxolan-4-yl) methyl methacrylate, stabilizers are added which prevent radical polymerization of the (meth) acrylic groups during the reaction. These stabilizers are well known in the art.
Eingesetzt werden hauptsächlich 1,4-Dihydroxybenzole. Es können jedoch auch anders substituierte Dihydroxybenzole zum Einsatz kommen. Allgemein lassen sich derartige Stabilisatoren mit der allgemeinen Formel (1) wiedergeben
- R5 einen linearen oder verzweigten Alkylrest mit eins bis acht Kohlenstoffatomen, Halogen oder Aryl bedeutet, vorzugsweise einen Alkylrest mit eins bis vier Kohlenstoffatomen, besonders bevorzugt Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec-Butyl, tert.-Butyl, Cl, F oder Br;
- o eine ganze Zahl im Bereich von eins bis vier, vorzugsweise eins oder zwei ist; und
- R6 Wasserstoff, einen linearen oder verzweigten Alkylrest mit eins bis acht Kohlenstoffatomen oder Aryl bedeutet, vorzugsweise einen Alkylrest mit eins bis vier Kohlenstoffatomen, besonders bevorzugt Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec-Butyl oder tert.-Butyl.
- R 5 is a linear or branched alkyl radical having one to eight carbon atoms, halogen or aryl, preferably an alkyl radical having one to four carbon atoms, more preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec Butyl, tert -butyl, Cl, F or Br;
- o is an integer in the range of one to four, preferably one or two; and
- R 6 is hydrogen, a linear or branched alkyl radical having one to eight carbon atoms or aryl, preferably an alkyl radical having one to four carbon atoms, particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec Butyl or tert-butyl.
Es können jedoch auch Verbindungen mit 1,4-Benzochinon als Stammverbindung eingesetzt werden. Diese lassen sich mit der Formel (11) beschreiben
- R5 einen linearen oder verzweigten Alkylrest mit eins bis acht Kohlenstoffatomen, Halogen oder Aryl bedeutet, vorzugsweise einen Alkylrest mit eins bis vier Kohlenstoffatomen, besonders bevorzugt Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec-Butyl, tert.-Butyl, Cl, F oder Br; und
- o eine ganze Zahl im Bereich von eins bis vier, vorzugsweise eins oder zwei ist.
- R 5 is a linear or branched alkyl radical having one to eight carbon atoms, halogen or aryl, preferably an alkyl radical having one to four carbon atoms, more preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec Butyl, tert -butyl, Cl, F or Br; and
- o is an integer in the range of one to four, preferably one or two.
Ebenso werden Phenole der allgemeinen Struktur (III) eingesetzt
- R5 einen linearen oder verzweigten Alkylrest mit eins bis acht Kohlenstoffatomen, Aryl oder Aralkyl, Propionsäureester mit 1 bis 4 wertigen Alkoholen, welche auch Heteroatome wie S, O und N enthalten können, vorzugsweise einen Alkylrest mit eins bis vier Kohlenstoffatomen, besonders bevorzugt Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec-Butyl, tert.-Butyl bedeutet.
- R 5 is a linear or branched alkyl radical having one to eight carbon atoms, aryl or aralkyl, propionic acid esters having 1 to 4 valent alcohols, which may also contain heteroatoms such as S, O and N, preferably an alkyl radical having one to four carbon atoms, particularly preferably methyl, Ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl.
Eine weitere vorteilhafte Substanzklasse stellen gehinderte Phenole auf Basis von Triazinderivaten der Formel (IV) dar
- R8 = CpH2p-1
- R 8 = C p H 2p - 1
Besonders erfolgreich werden die Verbindungen 1,4-Dihydroxybenzol, 4-Methoxyphenol, 2,5-Dichloro-3,6-dihydroxy-1,4-benzochinon, 1,3,5-Trimethyl-2,4,6-tris-(3,5-di-tert.butyl-4-hydroxybenzyl)benzol, 2,6-Di-tert. butyl-4-methylphenol, 2,4-Dimethyl-6-tert. butylphenol, 2,2-Bis [3,5-Bis(1,1-dimethylethyl)-4-hydroxyphenyl-1-oxopropoxymethyl)]1,3-propandiylester, 2,2'-Thiodiethylbis-[3-(3,5-di-tert.butyl-4-hydroxyphenyl)]propionat, Octadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)propionat, 3,5-Bis(1,1-dimethylethyl-2,2-Methylenbis-(4-methyl-6-tert.butyl)phenol, Tris-(4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazin-2,4,6-(1H,3H,5H)trion, Tris (3,5-ditert.butyl-4-hydroxy)-s-triazin-2,46-(1H, 3H,5H) trion oder tert Butyl-3,5-dihydroxybenzol, besonders bevorzugt 4-Hydroxy-2,2,6,6-tetramethylpiperidinooxyl, Hydrochinon, 4-Methyl-2,6-di-tert-butylphenol, Hydrochinonmonomethylether, 2-tert-Butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylat, 4-(Methacryloyloxy)-2,2,6,6-tetramethylpiperidin-1-oxyl oder 2,5-Di-tert-butylhydrochinon, eingesetzt.Particularly successful are the compounds 1,4-dihydroxybenzene, 4-methoxyphenol, 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone, 1,3,5-trimethyl-2,4,6-tris ( 3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,6-di-tert. butyl-4-methylphenol, 2,4-dimethyl-6-tert. butylphenol, 2,2-bis [3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl-1-oxopropoxymethyl)] 1,3-propanediyl ester, 2,2'-thiodiethylbis [3- (3,5 -di-tert-butyl-4-hydroxyphenyl)] propionate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,5-bis (1,1-dimethylethyl-2,2 -Methylenebis (4-methyl-6-tert-butyl) phenol, tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -s-triazine-2,4,6- (1H, 3H , 5H) trione, tris (3,5-di-tert-butyl-4-hydroxy) -s-triazine-2,46- (1H, 3H, 5H) -trione or tert-butyl-3,5-dihydroxybenzene, more preferably 4- Hydroxy-2,2,6,6-tetramethylpiperidinooxyl, hydroquinone, 4-methyl-2,6-di-tert-butylphenol, Hydroquinone monomethyl ether, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 4- (methacryloyloxy) -2,2,6,6-tetramethylpiperidine-1-oxyl or 2,5-di-tert-butylhydroquinone used.
Im Rahmen der Erfindung wird eine Tocopherolverbindung zur Stabilisierung von ethylenisch ungesättigten Monomeren verwendet.In the context of the invention, a tocopherol compound is used for the stabilization of ethylenically unsaturated monomers.
Bei den im Sinne der Erfindung verwendbaren Tocopherolverbindungen handelt es sich um in 2-Stellung mit einem 4,8,12-Trimethyltridecyl-Rest substituierte Chroman-6-ole (3,4-Dihydro-2H-1-benzopyran-6-ole). Zu den erfindungsgemäß vorzugsweise einsetzbaren Tocopherolen gehören alpha-Tocopherol, beta-Tocopherol, gamma-Tocopherol, delta-Tocopherol, zeta2-Tocopherol und eta-Tocopherol, alle der vorgenannten Verbindungen jeweils in der (2R, 4'R,8'R)-Form, sowie alpha-Tocopherol in der (all-rac)-Form. Bevorzugt sind alpha-Tocopherol in der (2R, 4'R,8'R)-Form (Trivialname: RRR-alpha-Tocopherol) sowie das synthetische racemische alpha-Tocopherol (all-rac-alpha-Tocopherol). Hiervon wiederum ist letztgenanntes aufgrund des relativ niedrigen Preises besonders interessant.In the usable according to the invention tocopherol is in 2-position by a 4,8,12-trimethyltridecyl radical substituted chroman-6-ols (3,4-dihydro-2 H- 1-benzopyran-6-ols ). The tocopherols which can preferably be used according to the invention include alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol, zeta2-tocopherol and eta-tocopherol, all of the abovementioned compounds in each case in the (2R, 4'R, 8'R) - Form, as well as alpha-tocopherol in the (all-rac) form. Preference is given to alpha-tocopherol in the (2R, 4'R, 8'R) form (common name: RRR-alpha-tocopherol) and also the synthetic racemic alpha-tocopherol (all-rac-alpha-tocopherol). Of these, in turn, the latter is particularly interesting because of the relatively low price.
Bezogen auf das Gewicht der gesamten Reaktionsmischung beträgt der Anteil der Stabilisatoren einzeln oder als Mischung im allgemeinen 0,01 - 0,50 Gew.-%, wobei man die Konzentration der Stabilisatoren vorzugsweise so auswählt, dass die Farbzahl gemäß DIN 55945 nicht beeinträchtigt wird. Viele dieser Stabilisatoren sind kommerziell erhältlich.Based on the weight of the total reaction mixture, the proportion of stabilizers individually or as a mixture is generally 0.01-0.50 wt .-%, wherein the concentration of the stabilizers is preferably selected so that the color number is not impaired according to DIN 55945. Many of these stabilizers are commercially available.
Glycerincarbonatmethacrylat kann als funktionelles Monomer in Copolymerisaten von Lacken und Klebstoffen verwendet werden, mit dem eine nachträgliche, polymeranaloge Reaktion, unter anderem die Vernetzung mit difunktionellen Aminen in einer Lackformulierung, möglich wird. Außerdem kann es in Batterie-Elektrolyten, Extrusionsharzen und zur Metallextraktion verwendet werden.Glycerol carbonate methacrylate can be used as a functional monomer in copolymers of paints and adhesives, with which a subsequent, polymer-analogous reaction, inter alia, the crosslinking with difunctional amines in a paint formulation, is possible. In addition, can it can be used in battery electrolytes, extrusion resins and for metal extraction.
Die im Folgenden gegebenen Beispiele werden zur besseren Veranschaulichung der vorliegenden Erfindung gegeben, sind jedoch nicht dazu geeignet, die Erfindung auf die hierin offenbarten Merkmale zu beschränken.The examples given below are given for a better illustration of the present invention, but are not intended to limit the invention to the features disclosed herein.
118 g (1,0 mol) Glycerincarbonat werden mit 600 g (6,0 mol) Methylmethacrylat und 0,14 g 4-Hydroxy-2,2,6,6-tetramethylpiperidinooxyl (Tempol) in einem Rundkolben mit Destillationsapparatur erwärmt. Eventuell vorhandenes Wasser wird azeotrop mit Methylmethacrylat abdestilliert. Anschließend wird die Mischung leicht abgekühlt. 18,0 g Zirkonacetylacetonat und die dem Azeotropdestillat äquivalente Menge Methylmethacrylat werden der Mischung zugefügt. Das Gemisch wird zum Sieden erhitzt. Die Alkoholyse wird bei 70°C Kopftemperatur begonnen. Gegen Ende der Reaktion erhöht sie sich auf 100°C.118 g (1.0 mol) of glycerol carbonate are heated with 600 g (6.0 mol) of methyl methacrylate and 0.14 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl (Tempol) in a round bottom flask with distillation apparatus. Any existing water is distilled off azeotropically with methyl methacrylate. The mixture is then cooled slightly. 18.0 g of zirconium acetylacetonate and the amount of methyl methacrylate equivalent to the azeotrope distillate are added to the mixture. The mixture is heated to boiling. The alcoholysis is started at 70 ° C head temperature. Towards the end of the reaction it increases to 100 ° C.
Nach Ende der Alkoholyse wird die Mischung abgekühlt und der Katalysator Zirkonacetylacetonat mit verdünnter Phosphorsäure gefällt. Anschließend wird die Suspension über einen Druckfilter gegeben und das Filtrat abgetrennt.After the end of the alcoholysis, the mixture is cooled and the catalyst zirconium acetylacetonate precipitated with dilute phosphoric acid. Subsequently, the suspension is passed through a pressure filter and the filtrate is separated.
Zur Abtrennung des Glycerincarbonats wird das Filtrat im Scheidetrichter mit einer verdünnten NaCl Lösung ausgeschüttelt. Das Filtrat wird am Rotationsverdampfer bei 70°C und 200-10 mbar entgast.To separate the glycerol carbonate, the filtrate is shaken out in a separating funnel with a dilute NaCl solution. The filtrate is degassed on a rotary evaporator at 70 ° C and 200-10 mbar.
Die Ausbeute beträgt 80,6%. Die Reinheit des Produktes 91,4%.
Versuchsnummer: B1The yield is 80.6%. The purity of the product 91.4%.
Test number: B1
236 g (2,0 mol) Glycerincarbonat werden mit 1200 g (12,0 mol) Methylmethacrylat und 0,29 g 4-Hydroxy-2,2,6,6-tetramethylpiperidinooxyl (Tempol) in einem Rundkolben mit Destillationsapparatur erwärmt. Eventuell vorhandenes Wasser wird azeotrop mit Methylmethacrylat abdestilliert. Anschließend wird die Mischung leicht abgekühlt. 28,7 g Zirkonacetylacetonat und die dem Azeotropdestillat äquivalente Menge Methylmethacrylat werden der Mischung zugefügt. Das Gemisch wird zum Sieden erhitzt. Die Alkoholyse wird bei 70°C Kopftemperatur begonnen. Gegen Ende der Reaktion erhöht sie sich auf 100°C.236 g (2.0 mol) of glycerol carbonate are heated with 1200 g (12.0 mol) of methyl methacrylate and 0.29 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl (Tempol) in a round bottom flask with distillation apparatus. Any existing water is distilled off azeotropically with methyl methacrylate. The mixture is then cooled slightly. 28.7 g of zirconium acetylacetonate and the amount of methyl methacrylate equivalent to the azeotrope distillate are added to the mixture. The mixture is heated to boiling. The alcoholysis is started at 70 ° C head temperature. Towards the end of the reaction it increases to 100 ° C.
Nach Ende der Alkoholyse wird die Mischung abgekühlt und der Katalysator Zirkonacetylacetonat mit verdünnter Phosphorsäure gefällt. Anschließend wird die Suspension über einen Druckfilter gegeben und das Filtrat abgetrennt.After the end of the alcoholysis, the mixture is cooled and the catalyst zirconium acetylacetonate precipitated with dilute phosphoric acid. Subsequently, the suspension is passed through a pressure filter and the filtrate is separated.
Zur Abtrennung des Glycerincarbonats wird das Filtrat im Scheidetrichter mit verdünnter NaCl Lösung ausgeschüttelt. Das Filtrat wird am Rotationsverdampfer bei 70°C und 200-10 mbar entgast.To separate the glycerol carbonate, the filtrate is shaken out in a separating funnel with dilute NaCl solution. The filtrate is degassed on a rotary evaporator at 70 ° C and 200-10 mbar.
Die Ausbeute beträgt 87,4%. Die Reinheit des Produktes 89,7%.
Versuchsnummer: B2The yield is 87.4%. The purity of the product 89.7%.
Test number: B2
236 g (2;0 mol) Glycerincarbonat werden mit 600 g (6,0 mol) Methylmethacrylat und 0,14 g 4-Hydroxy-2,2,6,6-tetramethylpiperidinooxyl (Tempol) in einem Rundkolben mit Destillationsapparatur erwärmt. Eventuell vorhandenes Wasser wird azeotrop mit Methylmethacrylat abdestilliert. Anschließend wird die Mischung leicht abgekühlt. 8,4 g lsopropyltitanat und die dem Azeotropdestillat äquivalente Menge Methylmethacrylat werden der Mischung zugefügt. Das Gemisch wird zum Sieden erhitzt. Die Alkoholyse wird bei 70°C Kopftemperatur begonnen. Die Reaktion ist aber sehr träge und wird deshalb nach 3 Stunden abgebrochen und überschüssiges Methylmethacrylat (MMA) abdestilliert. Der Rohester wird analytisch untersucht.
Versuchsnummer: V1236 g (2; 0 mol) of glycerol carbonate are heated with 600 g (6.0 mol) of methyl methacrylate and 0.14 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl (Tempol) in a round bottom flask with distillation apparatus. Any existing water is distilled off azeotropically with methyl methacrylate. Subsequently, the Mixture slightly cooled. 8.4 g of isopropyl titanate and the amount of methyl methacrylate equivalent to the azeotrope distillate are added to the mixture. The mixture is heated to boiling. The alcoholysis is started at 70 ° C head temperature. However, the reaction is very sluggish and is therefore terminated after 3 hours and distilled off excess methyl methacrylate (MMA). The crude ester is analyzed analytically.
Test number: V1
118 g (1,0 mol) Glycerincarbonat werden mit 600 g (6,0 mol) Methylmethacrylat und 0,14 g 4-Hydroxy-2,2,6,6-tetramethylpiperidinooxyl (Tempol) in einem Rundkolben mit Destillationsapparatur erwärmt. Eventuell vorhandenes Wasser wird azeotrop mit Methylmethacrylat abdestilliert. Anschließend wird die Mischung leicht abgekühlt. 14,4 g Dioctylzinnoxid und die dem Azeotropdestillat äquivalente Menge Methylmethacrylat werden der Mischung zugefügt. Das Gemisch wird zum Sieden erhitzt. Die Reaktion startet aber nicht, es bildet sich kein Methanol und der Versuch wird abgebrochen.
Versuchsnummer: V2118 g (1.0 mol) of glycerol carbonate are heated with 600 g (6.0 mol) of methyl methacrylate and 0.14 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl (Tempol) in a round bottom flask with distillation apparatus. Any existing water is distilled off azeotropically with methyl methacrylate. The mixture is then cooled slightly. 14.4 g of dioctyltin oxide and the amount of methyl methacrylate equivalent to the azeotrope distillate are added to the mixture. The mixture is heated to boiling. The reaction does not start, it does not form methanol and the attempt is terminated.
Experiment number: V2
118 g (1,0 mol) Glycerincarbonat werden mit 600 g (6,0 mol) Methylmethacrylat und 0,14 g 4-Hydroxy-2,2,6,6-tetramethylpiperidinooxyl (Tempol) in einem Rundkolben mit Destillationsapparatur erwärmt. Eventuell vorhandenes Wasser wird azeotrop mit Methylmethacrylat abdestilliert. Anschließend wird die Mischung leicht abgekühlt. 4,0 g LiOH, 10,4 g CaO und die dem Azeotropdestillat äquivalente Menge Methylmethacrylat werden der Mischung zugefügt. Das Gemisch wird zum Sieden erhitzt. Die Alkoholyse wird bei 70 °C Kopftemperatur begonnen. Gegen Ende der Reaktion erhöht sie sich auf 100 °C.118 g (1.0 mol) of glycerol carbonate are heated with 600 g (6.0 mol) of methyl methacrylate and 0.14 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl (Tempol) in a round bottom flask with distillation apparatus. Any existing water is distilled off azeotropically with methyl methacrylate. Subsequently, the Mixture slightly cooled. 4.0 g LiOH, 10.4 g CaO and the amount of methyl methacrylate equivalent to the azeotrope distillate are added to the mixture. The mixture is heated to boiling. The alcoholysis is started at 70 ° C head temperature. Towards the end of the reaction it increases to 100 ° C.
Anschließend wird der Ansatz abgekühlt, über einen Druckfilter gegeben und das Filtrat abgetrennt. Zur Abtrennung des Glycerincarbonats wird das Filtrat im Scheidetrichter mit verdünnter NaCl Lösung ausgeschüttelt. Das Filtrat wird am Rotationsverdampfer bei 70°C und 200-10 mbar entgast.The mixture is then cooled, passed through a pressure filter and the filtrate is separated. To separate the glycerol carbonate, the filtrate is shaken out in a separating funnel with dilute NaCl solution. The filtrate is degassed on a rotary evaporator at 70 ° C and 200-10 mbar.
Die Ausbeute beträgt 79,6%. Die Reinheit des Produktes 52,7%.
Versuchsnummer: V3The yield is 79.6%. The purity of the product 52.7%.
Test number: V3
118 g (1,0 mol) Glycerincarbonat werden mit 600 g (6,0 mol) Methylmethacrylat und 0,14 g 4-Hydroxy-2,2,6,6-tetramethylpiperidinooxyl (Tempol) in einem Rundkolben mit Destillationsapparatur erwärmt. Eventuell vorhandenes Wasser wird azeotrop mit Methylmethacrylat abdestilliert. Anschließend wird die Mischung leicht abgekühlt. 14,4 g Lithiummethylat und die dem Azeotropdestillat äquivalente Menge Methylmethacrylat werden der Mischung zugefügt. Das Gemisch wird zum Sieden erhitzt. Die Alkoholyse wird bei 70 °C Kopftemperatur begonnen. Gegen Ende der Reaktion erhöht sie sich diese auf 100 °C. Nach Beendigung der Reaktion wird überschüssiges MMA abdestilliert. Der Rohester wird filtriert und anschließend analytisch untersucht.
Versuchsnummer: V4118 g (1.0 mol) of glycerol carbonate are heated with 600 g (6.0 mol) of methyl methacrylate and 0.14 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl (Tempol) in a round bottom flask with distillation apparatus. Any existing water is distilled off azeotropically with methyl methacrylate. The mixture is then cooled slightly. 14.4 g of lithium methylate and the amount of methyl methacrylate equivalent to the azeotrope distillate are added to the mixture. The mixture is heated to boiling. The alcoholysis is started at 70 ° C head temperature. At the end of the reaction, it increases to 100 ° C. After completion of the reaction, excess MMA is distilled off. The crude ester is filtered and then analyzed analytically.
Test number: V4
Die Versuchsergebnisse werden in der nachfolgenden Tabelle zusammengefasst:
* berücksichtigt HS 2 Glycerintrimethacrylat n.b. nicht bestimmt
* does not consider HS 2 glycerol trimethacrylate nb determined
Claims (8)
- Process for preparing (2-oxo-1,3-dioxolan-4-yl)-methyl methacrylate, characterized in that methyl methacrylate is transesterified with glycerol carbonate in the presence of stabilizers and a metal chelate catalyst of the metal ion 1,3-diketonate type.
- Process for preparing (2-oxo-1,3-dioxolan-4-yl)-methyl methacrylate, characterized in that the catalyst is zirconium acetylacetonate.
- Process for preparing (2-oxo-1,3-dioxolan-4-yl)-methyl methacrylate, characterized in that the transesterification takes place at 50-80°C.
- Process for preparing (2-oxo-1,3-dioxolan-4-yl)-methyl methacrylate, characterized in that the transesterification takes place at 70°C.
- Process for preparing (2-oxo-1,3-dioxolan-4-yl)-methyl methacrylate, characterized in that zirconium acetylacetonate is used in amounts of 0.1-5.0% by weight, based on the total weight of the batch.
- Process for preparing (2-oxo-1,3-dioxolan-4-yl)-methyl methacrylate, characterized in that zirconium acetylacetonate is used in amounts of 1.0-3.0% by weight, based on the total weight of the batch.
- Process for preparing (2-oxo-1,3-dioxolan-4-yl)-methyl methacrylate, characterized in that the amount of crosslinker formed during the preparation is less than 5% by weight, in particular less than 3% by weight.
- Process for preparing (2-oxo-1,3-dioxolan-4-yl)-methyl methacrylate, characterized in that stabilizers are used in amounts of 0.01-0.50% by weight.
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DE10355830A DE10355830A1 (en) | 2003-11-26 | 2003-11-26 | Production of (2-oxo-1,3-dioxolan-4-yl)-methyl methacrylate for use e.g. in adhesives or paint, comprises transesterification of methyl methacrylate with glycerol carbonate using a metal 1,3-diketonate catalyst |
PCT/EP2004/009423 WO2005058862A2 (en) | 2003-11-26 | 2004-08-24 | Method for producing glycerol carbonate methacrylate |
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EP (1) | EP1689735B1 (en) |
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EP1894922A1 (en) * | 2006-06-22 | 2008-03-05 | Cognis GmbH | Process for the preparation of glycerincarbonate esters |
EP1870407A1 (en) * | 2006-06-22 | 2007-12-26 | Cognis Oleochemicals GmbH | Process for the preparation of glycerincarbonate esters |
ES2554983T3 (en) * | 2007-04-03 | 2015-12-28 | Henkel Ag & Co. Kgaa | Grating inhibitor washing agent |
EP2487232B1 (en) * | 2007-04-03 | 2014-12-03 | Henkel AG & Co. KGaA | Cleaning agent |
CN102260128A (en) * | 2010-05-25 | 2011-11-30 | 南京凯时通新材料有限公司 | Process for preparing acrylate monomer and derivative thereof by using transesterification method |
DE102011109139A1 (en) | 2011-08-02 | 2013-02-07 | Evonik Röhm Gmbh | Low-odor (meth) acrylic reaction resins |
TWI806890B (en) | 2017-08-17 | 2023-07-01 | 德商巴斯夫歐洲公司 | Preparation of (meth)acrylates of glycerol carbonate |
FR3084370B1 (en) * | 2018-07-24 | 2021-03-05 | Jacret | COMPOSITION FOR STRUCTURAL ADHESIVE |
JP7094493B2 (en) * | 2018-08-03 | 2022-07-04 | 日油株式会社 | Method for Producing Cyclocarbonate Group-Containing (Meta) Acrylate Monomer |
NL2023314B1 (en) | 2019-03-21 | 2020-09-28 | Illumina Inc | Artificial intelligence-based quality scoring |
NL2023310B1 (en) | 2019-03-21 | 2020-09-28 | Illumina Inc | Training data generation for artificial intelligence-based sequencing |
US20220388943A1 (en) | 2019-10-23 | 2022-12-08 | Evonik Operations Gmbh | Process for preparing glycerol carbonate (meth)acrylate |
EP4092056A4 (en) * | 2020-01-15 | 2023-11-22 | NOF Corporation | Cyclocarbonate group-containing (meth)acrylate monomer and polymer |
CN112186261A (en) * | 2020-10-09 | 2021-01-05 | 天津大学 | Method for self-supporting all-solid-state electrolyte battery of polyester type by in-situ polymerization |
WO2023049212A2 (en) | 2021-09-22 | 2023-03-30 | Illumina, Inc. | State-based base calling |
WO2023242258A1 (en) | 2022-06-15 | 2023-12-21 | Evonik Operations Gmbh | Method for (trans)esterification of (meth)acrylate compounds using strong basic catalysts |
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GB1573071A (en) * | 1977-02-10 | 1980-08-13 | Mitsubishi Rayon Co | Process for producing unsaturated carbocylic acid esters |
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JP2003327854A (en) * | 2002-05-09 | 2003-11-19 | Japan Paint Manufacturers Association | Aqueous curable resin composition |
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DE10355830A1 (en) | 2005-06-09 |
DE502004005991D1 (en) | 2008-03-06 |
CN100519547C (en) | 2009-07-29 |
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CN1886395A (en) | 2006-12-27 |
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